Bridged bi-aromatic ligands and olefin polymerization catalysts prepared therefrom

ABSTRACT

Disclosed are novel bridged bi-aromatic phenol ligands and transition metal catalyst compounds derived therefrom. Also disclosed are methods of making the ligands and transition metal compounds, and polymerization processes utilizing the transition metal compounds for the production of olefin polymers.

This application is a continuation application of U.S. Ser. No.15/567,713, filed Oct. 19, 2017 and published as U.S. Publication No.2018-0147562 A1 on May 31, 2018, which is a National Stage Applicationunder 35 U.S.C. § 371 of International Application NumberPCT/US2016/028268, filed Apr. 19, 2016 and published as WO 2016/172097on Oct. 27, 2016, which claims the benefit to U.S. ProvisionalApplication 62/150,124, filed Apr. 20, 2015, the entire contents ofwhich are incorporated herein by reference in its entirety.

FIELD

The present disclosure is directed to bridged bi-aromatic ligands andtransition metal compounds prepared therefrom. The disclosure is alsodirected to methods of preparing the ligands and transition metalcompounds, and to methods of using the transition metal compounds ascatalyst components in olefin polymerization.

BACKGROUND

A major focus of the polyolefin industry in recent years has been on thedevelopment of new catalysts that deliver new and improved products.Bulky ligand transition metal compounds, for example, are now widelyutilized in catalyst compositions to produce polyolefin polymers, suchas polyethylene polymers.

It is recognized in the art that small differences in the molecularstructure of a catalyst compound can greatly impact catalyst performanceand that this is often governed by ligand structure. Thereforeconsiderable effort has been expended in designing new ligand structuresthat may lead to catalysts of enhanced performance. WO 03/09162discloses bridged bi-aromatic ligands, methods for their preparation andtransition metal compounds derived therefrom.

It would be desirable to provide new bridged bi-aromatic ligands andmethods for their synthesis. It would also be desirable to provide newtransition metal compounds that can polymerize olefins with usefulactivity.

SUMMARY

In one aspect there is provided a bridged bi-aromatic phenol ligand offormula (I):

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² isindependently selected from the group consisting of hydride, halide,optionally substituted hydrocarbyl, heteroatom-containing optionallysubstituted hydrocarbyl, alkoxy, aryloxy, silyl, boryl, dialkyl amino,alkylthio, arylthio and seleno; optionally two or more R groups cancombine together into ring structures with such ring structures havingfrom 3 to 100 non-hydrogen atoms in the ring; A is a bridging grouphaving from one to 50 non-hydrogen atoms; Y and Y′ are independentlyselected from O, S, NR^(a) and PR^(a) wherein R^(a) is optionallysubstituted hydrocarbyl; Ar is, independently, optionally substitutedaryl or optionally substituted heteroaryl.

Each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² may beindependently selected from the group consisting of hydride, halide, andoptionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxyl,aryloxyl, silyl, boryl, dialkylamino, alkylthio, arylthio and seleno.

Each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² may beindependently selected from the group consisting of hydride, halide, andoptionally substituted alkyl, heteroalkyl, aryl, heteroaryl, alkoxyl andaryloxyl.

Each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² may beindependently selected from the group consisting of hydride, fluoro,chloro, and optionally substituted alkyl, heteroalkyl, aryl andheteroaryl.

In any one of the hereinbefore embodiments the bridging group A may beselected from the group consisting of optionally substituted divalenthydrocarbyl and divalent heteroatom containing hydrocarbyl.

In any one of the hereinbefore disclosed embodiments the bridging groupA may be selected from the group consisting of optionally substituteddivalent alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl,heteroalkynyl, aryl, heteroaryl and silyl.

In any one of the hereinbefore disclosed embodiments the bridging groupA may be represented by the general formula -(QR¹³ _(2−z″))_(z′)—wherein each Q is either carbon or silicon and each R¹³ may be the sameor different from the others such that each R¹³ is selected from thegroup consisting of hydride and optionally substituted hydrocarbyl andheteroatom containing hydrocarbyl, and optionally two or more R¹³ groupsmay be joined into a ring structure having from 3 to 50 atoms in thering structure not counting hydrogen atoms; z′ is an integer from 1 to10; and z″ is 0, 1 or 2.

In any one of the hereinbefore disclosed embodiments Ar may be,independently, an optionally substituted phenyl, naphthyl, biphenyl,anthracenyl or phenanthrenyl.

In any one of the hereinbefore disclosed embodiments Ar may be,independently, an optionally substituted thiophene, pyridine, isoxazole,pyrazole, pyrrole, furan, or benzo-fused analogues of these rings.

In any one of the hereinbefore disclosed embodiments each occurrence ofAr is the same.

The bridged bi-aromatic phenol ligand of formula (I) may be of formula(II):

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², Arand A is as defined in any one of the hereinbefore disclosedembodiments.

In another aspect there is provided a method for preparing a bridgedbi-aromatic phenol ligand of formula (I) or formula (II) the methodcomprising at least one step of halogenation of an aromatic ring and atleast one step of aryl coupling.

The method may comprise at least one step of Negishi coupling. Themethod may comprise at least one step of Suzuki coupling. The method maycomprise both at least one step of Negishi coupling and at least onestep of Suzuki coupling.

The method may comprise the steps of:

-   -   a) treating a bridged bi-aromatic phenol of formula (III) with a        source of halogen to yield a tetrahalo bridged bi-aromatic        phenol of formula (IV); and

-   -   b) treating the tetrahalo bridged bi-aromatic phenol of        formula (IV) with an aryl-boron compound (ArBR^(b) ₂ or ArBF₃        ⁻M⁺⁾ in the presence of a catalyst, to yield the bridged        bi-aromatic phenol ligand of formula (I);        wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and        R¹² is independently selected from the group consisting of        hydride, halide, optionally substituted hydrocarbyl,        heteroatom-containing optionally substituted hydrocarbyl,        alkoxy, aryloxy, silyl, boryl, dialkyl amino, alkylthio,        arylthio and seleno; optionally two or more R¹ to R¹² groups can        combine together into ring structures with such ring structures        having from 3 to 100 non-hydrogen atoms in the ring; A is a        bridging group having from one to 50 non-hydrogen atoms; Y and        Y′ are independently selected from O, S, NR^(a) and PR^(a)        wherein R^(a) is optionally substituted hydrocarbyl; Ar is,        independently, optionally substituted aryl or optionally        substituted heteroaryl; X is halo; R^(b) is independently        selected from hydride, alkyl, hydroxy and alkoxy, wherein when        both of R^(b) are alkoxy, optionally they may combine to form a        ring structure of formula BO₂R^(b) ₂, and wherein M⁺ is an        alkali metal cation.

The method may comprise the steps of:

-   -   a) treating a halophenol of formula (V) with a bridged diboron        compound of formula (VI) in the presence of a catalyst to yield        the bridged bi-aromatic phenol of formula (III);

-   -   b) treating the bridged bi-aromatic phenol of formula (III) with        a source of halogen to yield a tetrahalo bridged bi-aromatic        phenol of formula (IV); and    -   c) treating the tetrahalo bridged bi-aromatic phenol of        formula (IV) with an aryl-boron compound (ArBR^(b) ₂ or ArBF₃        ⁻M⁺) in the presence of a catalyst, to yield the bridged        bi-aromatic phenol ligand of formula (I);        wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and        R¹² is independently selected from the group consisting of        hydride, halide, optionally substituted hydrocarbyl,        heteroatom-containing optionally substituted hydrocarbyl,        alkoxy, aryloxy, silyl, boryl, dialkyl amino, alkylthio,        arylthio and seleno; optionally two or more R groups can combine        together into ring structures with such ring structures having        from 3 to 100 non-hydrogen atoms in the ring; A is a bridging        group having from one to 50 non-hydrogen atoms; Y and Y′ are        independently selected from O, S, NR^(a) and PR^(a) wherein        R^(a) is optionally substituted hydrocarbyl; Z and Z′ are        independently selected from BR^(b) ₂ and BF₃ ⁻M⁺, wherein R^(b)        is independently selected from hydride, alkyl, hydroxy and        alkoxy, wherein when both of R^(b) are alkoxy, optionally they        may combine to form a ring structure of formula BO₂R^(b) ₂, and        wherein M⁺ is an alkali metal cation; Ar is, independently,        optionally substituted aryl or optionally substituted        heteroaryl; X is halo.

In any one of the hereinbefore disclosed embodiments each of R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² may be independently selectedfrom the group consisting of hydride, halide, and optionally substitutedalkyl, heteroalkyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl,dialkylamino, alkylthio, arylthio and seleno.

In any one of the hereinbefore disclosed embodiments each of R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹, and R¹² may be independently selectedfrom the group consisting of hydride, halide, and optionally substitutedalkyl, heteroalkyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl,dialkylamino, alkylthio, and arylthio.

In any one of the hereinbefore disclosed embodiments the bridging groupA may be selected from the group consisting of optionally substituteddivalent hydrocarbyl and divalent heteroatom containing hydrocarbyl.

In any one of the hereinbefore disclosed embodiments the bridging groupA may be selected from the group consisting of optionally substituteddivalent alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl,heteroalkynyl, carbocycle, heterocarbocycle, aryl, heteroaryl and silyl.

In any one of the hereinbefore disclosed embodiments the bridging groupA may be represented by the general formula -(QR¹³ _(2−z″))_(z′)—wherein each Q is either carbon or silicon and each R¹³ may be the sameor different from the others such that each R¹³ is selected from thegroup consisting of hydride and optionally substituted hydrocarbyl andheteroatom containing hydrocarbyl, and optionally two or more R¹³ groupsmay be joined into a ring structure having from 3 to 50 atoms in thering structure not counting hydrogen atoms; z′ is an integer from 1 to10; and z″ is 0, 1 or 2.

A major advantage of the herein disclosed methods is that the number ofreaction steps to access the ligands is low. For example, the disclosedligands may be prepared from a bromophenol in three or four reactionsteps.

In any one of the hereinbefore disclosed embodiments the catalyst maycomprise a palladium or nickel catalyst.

In any one of the hereinbefore disclosed embodiments the palladiumcatalyst may comprise a palladium phosphine catalyst.

In any one of the hereinbefore disclosed embodiments the catalyst mayfurther comprise a base.

In any one of the hereinbefore disclosed embodiments the base maycomprise an alkali metal carbonate, alkali metal phosphate, alkali metalhydroxide, alkali metal alkoxide or an amine.

In any one of the hereinbefore disclosed embodiments X may be bromo orchloro. The source of halogen may be bromine or chlorine.

In any one of the hereinbefore disclosed embodiments the aryl-boroncompound may be an optionally substituted arylborane or an optionallysubstituted heteroarylborane.

In any one of the hereinbefore disclosed embodiments the aryl-boroncompound may be an optionally substituted aryl boronic acid or anoptionally substituted heteroaryl boronic acid.

In any one of the hereinbefore disclosed embodiments the aryl-boroncompound may be an optionally substituted aryl boronic ester or arylcyclic boronic ester or an optionally substituted heteroaryl boronicester or hetero aryl cyclic boronic ester.

In any one of the hereinbefore disclosed embodiments the aryl-boroncompound may be an optionally substituted aryl trifluoroborate or anoptionally substituted heteroaryl trifluoroborate.

In another aspect there is provided a ligand of formula (I) or formula(II) prepared by any one of the hereinbefore disclosed methods.

In another aspect there is provided a transition metal compound formedfrom any one of the hereinbefore disclosed ligands. The transition metalcompound may comprise a titanium, a zirconium or a hafnium atom.

In another aspect there is provided a catalyst composition comprisingone or more transition metal compounds as hereinbefore disclosed, andone or more activators. The activator may comprise one or morealumoxanes. The activator may comprise methylalumoxane.

In another aspect there is provided a supported catalyst compositioncomprising one or more transition metal compounds as hereinbeforedisclosed, one or more activators and one or more support materials. Theactivator may comprise one or more alumoxanes. The activator maycomprise methylalumoxane. The support may be silica.

The catalyst composition or supported catalyst composition may comprisetwo or more transition metal compounds. The transition metal compoundsmay be selected from any one of those hereinbefore disclosed or at leastone of the transition metal compounds may be different from thosehereinbefore disclosed. For example, at least one of the transitionmetal compounds may be a metallocene.

In another aspect there is provided a process for polymerizing olefins,the process comprising:

contacting olefins with one or more catalyst compositions or supportedcatalyst compositions comprising at least one transition metal compoundas hereinbefore disclosed in a reactor under polymerization conditionsto produce an olefin polymer or copolymer

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 depict the chemical structures of exemplary compounds inaccordance with the present disclosure.

FIGS. 3 to 5 depict exemplary reaction schemes in accordance with thepresent disclosure.

DETAILED DESCRIPTION

Before the present compounds, components, compositions, and/or methodsare disclosed and described, it is to be understood that unlessotherwise indicated this invention is not limited to specific compounds,components, compositions, reactants, reaction conditions, ligands,transition metal compounds, or the like, as such may vary, unlessotherwise specified. It is also to be understood that the terminologyused herein is for the purpose of describing particular embodiments onlyand is not intended to be limiting.

It must also be noted that, as used in the specification and theappended claims, the singular forms “a,” “an” and “the” include pluralreferents unless otherwise specified. Thus, for example, reference to “ahalogen atom” as in a moiety “substituted with a halogen atom” includesmore than one halogen atom, such that the moiety may be substituted withtwo or more halogen atoms, reference to “a substituent” includes one ormore substituents, reference to “a ligand” includes one or more ligands,and the like.

As used herein, all reference to the Periodic Table of the Elements andgroups thereof is to the NEW NOTATION published in HAWLEY'S CONDENSEDCHEMICAL DICTIONARY, Thirteenth Edition, John Wiley & Sons, Inc., (1997)(reproduced there with permission from IUPAC), unless reference is madeto the Previous IUPAC form noted with Roman numerals (also appearing inthe same), or unless otherwise noted.

Disclosed herein are ligands, catalyst compounds, catalyst compositionsand supported catalyst compositions for use in the polymerization ofolefins which are advantageous to prepare and use. Also disclosed hereinare methods of making the ligands, catalyst compounds, catalystcompositions and supported catalyst compositions and polymerizationprocesses utilizing the catalyst compositions and supported catalystcompositions for the production of olefin polymers.

General Definitions

As used herein, a “catalyst composition” includes one or more catalystcompounds utilized to polymerize olefins and at least one activator or,alternatively, at least one cocatalyst. The catalyst composition mayinclude any suitable number of catalyst compounds in any combination asdescribed herein, as well as any activator or cocatalyst in anycombination as described herein.

As used herein, a “supported catalyst composition” includes one or morecatalyst compounds utilized to polymerize olefins and at least oneactivator or, alternatively, at least one cocatalyst, and at least onesupport. The supported catalyst composition may include any suitablenumber of catalyst compounds in any combination as described herein, aswell as any activator or cocatalyst in any combination as describedherein. A “supported catalyst composition” may also contain one or moreadditional components known in the art to reduce or eliminate reactorfouling such as continuity additives.

As used herein, a “catalyst compound” may include any compound that,when activated, is capable of catalyzing the polymerization oroligomerization of olefins, wherein the catalyst compound comprises atleast one Group 3 to 12 atom, and optionally at least one leaving groupbound thereto.

The term “independently selected” is used herein to indicate that the Rgroups, e.g., R¹, R², R³, R⁴, and R⁵ can be identical or different (e.g.R¹, R², R³, R⁴, and R⁵ may all be substituted alkyls or R¹ and R² may bea substituted alkyl and R³ may be an aryl, etc.). Use of the singularincludes use of the plural and vice versa (e.g., a hexane solvent,includes hexanes). A named R group will generally have the structurethat is recognized in the art as corresponding to R groups having thatname. The terms “compound” and “complex” are generally usedinterchangeably in this specification, but those of skill in the art mayrecognize certain compounds as complexes and vice versa. For thepurposes of illustration, representative certain groups are definedherein. These definitions are intended to supplement and illustrate, notpreclude, the definitions known to those of skill in the art.

“Optional” or “optionally” means that the subsequently described eventor circumstance may or may not occur, and that the description includesinstances where said event or circumstance occurs and instances where itdoes not. For example, the phrase “optionally substituted hydrocarbyl”means that a hydrocarbyl moiety may or may not be substituted and thatthe description includes both unsubstituted hydrocarbyl and hydrocarbylwhere there is substitution.

The term “alkyl” as used herein refers to a branched or unbranchedsaturated hydrocarbon group typically although not necessarilycontaining 1 to about 50 carbon atoms, such as methyl, ethyl, n-propyl,isopropyl, n-butyl, iso-butyl, t-butyl, octyl, decyl, and the like, aswell as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like.Generally, although again not necessarily, alkyl groups herein maycontain 1 to about 12 carbon atoms. The term “lower alkyl” intends analkyl group of one to six carbon atoms, specifically one to four carbonatoms. “Substituted alkyl” refers to alkyl substituted with one or moresubstituent groups (e.g., benzyl or chloromethyl), and the terms“heteroatom-containing alkyl” and “heteroalkyl” refer to alkyl in whichat least one carbon atom is replaced with a heteroatom (e.g., —CH₂OCH₃is an example of a heteroalkyl).

The term “alkenyl” as used herein refers to a branched or unbranchedhydrocarbon group typically although not necessarily containing 2 toabout 50 carbon atoms and at least one double bond, such as ethenyl,n-propenyl, iso-propenyl, n-butenyl, iso-butenyl, octenyl, decenyl, andthe like. Generally, although again not necessarily, alkenyl groupsherein contain 2 to about 12 carbon atoms. The term “lower alkenyl”refers to an alkenyl group of two to six carbon atoms, specifically twoto four carbon atoms. “Substituted alkenyl” refers to alkenylsubstituted with one or more substituent groups, and the terms“heteroatom-containing alkenyl” and “heteroalkenyl” refer to alkenyl inwhich at least one carbon atom is replaced with a heteroatom.

The term “alkynyl” as used herein refers to a branched or unbranchedhydrocarbon group typically although not necessarily containing 2 toabout 50 carbon atoms and at least one triple bond, such as ethynyl,n-propynyl, iso-propynyl, n-butynyl, isobutynyl, octynyl, decynyl, andthe like. Generally, although again not necessarily, alkynyl groupsherein may have 2 to about 12 carbon atoms. The term “lower alkynyl”refers to an alkynyl group of two to six carbon atoms, specificallythree or four carbon atoms. “Substituted alkynyl” refers to alkynylsubstituted with one or more substituent groups, and the terms“heteroatom-containing alkynyl” and “heteroalkynyl” refer to alkynyl inwhich at least one carbon atom is replaced with a heteroatom.

The term “alkoxy” as used herein intends an alkyl group bound through asingle, terminal ether linkage; that is, an “alkoxy” group may berepresented as —O-alkyl where alkyl is as defined above. A “loweralkoxy” group refers to an alkoxy group having one to six, morespecifically one to four, carbon atoms. The term “aryloxy” is used in asimilar fashion, with aryl as defined below. The term “hydroxy” refersto —OH.

Similarly, the term “alkylthio” as used herein intends an alkyl groupbound through a single, terminal thioether linkage; that is, an“alkylthio” group may be represented as —S-alkyl where alkyl is asdefined above. A “lower alkyl thio” group refers to an alkyl thio grouphaving one to six, more specifically one to four, carbon atoms. The term“arylthio” is used similarly, with aryl as defined below. The term“thioxy” refers to —SH.

The term “allenyl” is used herein in the conventional sense to refer toa molecular segment having the structure —CH═C═CH₂. An “allenyl” groupmay be unsubstituted or substituted with one or more non-hydrogensubstituents.

The term “aryl” as used herein, and unless otherwise specified, refersto an aromatic substituent containing a single aromatic ring or multiplearomatic rings that are fused together, linked covalently, or linked toa common group such as a methylene or ethylene moiety. More specificaryl groups contain one aromatic ring or two or three fused or linkedaromatic rings, e.g., phenyl, naphthyl, biphenyl, anthracenyl,phenanthrenyl, and the like. The aryl substituents may have 1 to about200 carbon atoms, typically 1 to about 50 carbon atoms, and specifically1 to about 20 carbon atoms. “Substituted aryl” refers to an aryl moietysubstituted with one or more substituent groups, (e.g., tolyl, mesityland perfluorophenyl) and the terms “heteroatom-containing aryl” and“heteroaryl” refer to aryl in which at least one carbon atom is replacedwith a heteroatom (e.g., rings such as thiophene, pyridine, isoxazole,pyrazole, pyrrole, furan, etc. or benzo-fused analogues of these ringsare included in the term “heteroaryl”). In some embodiments herein,multi-ring moieties are substituents and in such an embodiment themulti-ring moiety can be attached at an appropriate atom. For example,“naphthyl” can be 1-naphthyl or 2-naphthyl; “anthracenyl” can be1-anthracenyl, 2-anthracenyl or 9-anthracenyl; and “phenanthrenyl” canbe 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl or9-phenanthrenyl.

The term “aralkyl” refers to an alkyl group with an aryl substituent,and the term “aralkylene” refers to an alkylene group with an arylsubstituent; the term “alkaryl” refers to an aryl group that has analkyl substituent, and the term “alkarylene” refers to an arylene groupwith an alkyl substituent.

The terms “halo” and “halogen” are used in the conventional sense torefer to a chloro, bromo, fluoro or iodo substituent. The terms“haloalkyl,” “haloalkenyl” or “haloalkynyl” (or “halogenated alkyl,”“halogenated alkenyl,” or “halogenated alkynyl”) refers to an alkyl,alkenyl or alkynyl group, respectively, in which at least one of thehydrogen atoms in the group has been replaced with a halogen atom.

The term “heteroatom-containing” as in a “heteroatom-containinghydrocarbyl group” refers to a molecule or molecular fragment in whichone or more carbon atoms is replaced with an atom other than carbon,e.g., nitrogen, oxygen, sulfur, phosphorus, boron or silicon. Similarly,the term “heteroalkyl” refers to an alkyl substituent that isheteroatom-containing, the term “heterocyclic” refers to a cyclicsubstituent that is heteroatom-containing, the term “heteroaryl” refersto an aryl substituent that is heteroatom-containing, and the like. Whenthe term “heteroatom-containing” appears prior to a list of possibleheteroatom-containing groups, it is intended that the term apply toevery member of that group. That is, the phrase “heteroatom-containingalkyl, alkenyl and alkynyl” is to be interpreted as“heteroatom-containing alkyl, heteroatom-containing alkenyl andheteroatom-containing alkynyl.”

“Hydrocarbyl” refers to hydrocarbyl radicals containing 1 to about 50carbon atoms, specifically 1 to about 24 carbon atoms, most specifically1 to about 16 carbon atoms, including branched or unbranched, saturatedor unsaturated species, such as alkyl groups, alkenyl groups, arylgroups, and the like. The term “lower hydrocarbyl” refers to ahydrocarbyl group of one to six carbon atoms, specifically one to fourcarbon atoms. “Substituted hydrocarbyl” refers to hydrocarbylsubstituted with one or more substituent groups, and the terms“heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer tohydrocarbyl in which at least one carbon atom is replaced with aheteroatom.

By “substituted” as in “substituted hydrocarbyl,” “substituted aryl,”“substituted alkyl,” “substituted alkenyl” and the like, as alluded toin some of the aforementioned definitions, is meant that in thehydrocarbyl, hydrocarbylene, alkyl, alkenyl, aryl or other moiety, atleast one hydrogen atom bound to a carbon atom is replaced with one ormore substituents that are functional groups such as hydroxyl, alkoxy,alkylthio, phosphino, amino, halo, silyl, and the like. When the term“substituted” appears prior to a list of possible substituted groups, itis intended that the term apply to every member of that group. That is,the phrase “substituted alkyl, alkenyl and alkynyl” is to be interpretedas “substituted alkyl, substituted alkenyl and substituted alkynyl.”Similarly, “optionally substituted alkyl, alkenyl and alkynyl” is to beinterpreted as “optionally substituted alkyl, optionally substitutedalkenyl and optionally substituted alkynyl.”

By “divalent” as in “divalent hydrocarbyl”, “divalent alkyl”, “divalentaryl” and the like, is meant that the hydrocarbyl, alkyl, aryl or othermoiety is bonded at two points to atoms, molecules or moieties with thetwo bonding points being covalent bonds. The term “aromatic” is used inits usual sense, including unsaturation that is essentially delocalizedacross multiple bonds, such as around a ring.’

As used herein the term “silyl” refers to the —SiZ¹Z²Z³ radical, whereeach of Z¹, Z², and Z³ is independently selected from the groupconsisting of hydride and optionally substituted alkyl, alkenyl,alkynyl, heteroatom-containing alkyl, heteroatom-containing alkenyl,heteroatom-containing alkynyl, aryl, heteroaryl, alkoxy, aryloxy, amino,silyl and combinations thereof.

As used herein the term “boryl” refers to the —BZ¹Z² group, where eachof Z¹ and Z² is as defined above.

As used herein, the term “phosphino” refers to the group —PZ¹Z², whereeach of Z¹ and Z² is as defined above. As used herein, the term“phosphine” refers to the group PZ¹Z²Z³, where each of Z¹, Z² and Z³ isas defined above. The term “amino” is used herein to refer to the group—NZ¹Z², where each of Z¹ and Z² is as defined above. The term “amine” isused herein to refer to the group NZ¹Z²Z³, where each of Z¹, Z² and Z³is as defined above.

The term “saturated” refers to lack of double and triple bonds betweenatoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, andthe like. The term “unsaturated” refers to the presence of one or moredouble and triple bonds between atoms of a radical group such as vinyl,acetylide, oxazolinyl, cyclohexenyl, acetyl and the like.

Other abbreviations used herein include: “iPr” to refer to isopropyl;“tBu” to refer to tertbutyl; “Me” to refer to methyl; “Et” to refer toethyl; and “Ph” refers to phenyl.

The bridged bi-aromatic ligands disclosed herein have the followinggeneral formula (I):

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² isindependently selected from the group consisting of hydride, halide,optionally substituted hydrocarbyl, heteroatom-containing optionallysubstituted hydrocarbyl, alkoxy, aryloxy, silyl, boryl, dialkyl amino,alkylthio, arylthio and seleno; optionally two or more R groups cancombine together into ring structures with such ring structures havingfrom 3 to 100 non-hydrogen atoms in the ring; A is a bridging grouphaving from one to 50 non-hydrogen atoms; Y and Y′ are independentlyselected from O, S, NR^(a) and PR^(a) wherein R^(a) is optionallysubstituted hydrocarbyl; Ar is, independently, optionally substitutedaryl or optionally substituted heteroaryl.

The ligands may also have the following formula (II):

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² isindependently selected from the group consisting of hydride, halide,optionally substituted hydrocarbyl, heteroatom-containing optionallysubstituted hydrocarbyl, alkoxy, aryloxy, silyl, boryl, dialkyl amino,alkylthio, arylthio and seleno; optionally two or more R groups cancombine together into ring structures with such ring structures havingfrom 3 to 100 non-hydrogen atoms in the ring; A is a bridging grouphaving from one to 50 non-hydrogen atoms; Ar is, independently,optionally substituted aryl or optionally substituted heteroaryl.

Each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² may behydride or optionally substituted alkyl or aryl. R² and R⁸ may beoptionally substituted alkyl and each of R¹, R³, R⁴, R⁵, R⁶, R⁷, R⁹,R¹⁰, R¹¹ and R¹² may be hydride.

The bridging group A may be optionally substituted alkyl.

Ar may be optionally substituted phenyl, naphthyl, biphenyl,anthracenyl, phenanthrenyl or optionally substituted thiophene,pyridine, isoxazole, pyrazole, pyrrole, furan, etc. or benzo-fusedanalogues. The optional substituents may be alkyl groups.

The ligands may have the following structure:

wherein Ar may be optionally substituted phenyl, naphthyl, biphenyl,anthracenyl, phenanthrenyl or optionally substituted thiophene,pyridine, isoxazole, pyrazole, pyrrole, furan, or benzo-fused analoguesand the bridging group A is a divalent alkyl.

R₂ and R₈ may be optionally substituted alkyl.

The ligands may have the following structure:

wherein Rx, R₂ and R₈ are alkyl, and n=0 to 6.

Specific ligands disclosed herein include:

Ligand Synthesis

The ligands disclosed herein may be prepared by a variety of methods. Ingeneral the ligands may be prepared by employing a tetrabromination of abridged phenyl phenol and aryl coupling. The aryl coupling may be Suzukicoupling and/or Negishi coupling.

A major advantage of the herein disclosed methods is that the number ofreaction steps to access the ligands is low. For example, the disclosedligands may be prepared from a bromophenol in three or four reactionsteps.

Bridged bi-aromatic ligand syntheses disclosed in WO 03/09162 sufferfrom an abundance of synthetic steps which add time and cost to asynthesis. Suzuki couplings disclosed in WO 03/091162 were performed onprotected phenols (THP, Bn, MOM, etc), which add steps due to therequired protections and deprotections. However, given the proticsolvents used in these reactions, it was hypothesized that a free phenolwould not interfere with coupling. Indeed, a Suzuki coupling withbromocresol and phenyl boronic acid was successful and high yielding.Other boronic acids were also coupled to bromocresol without difficultyas shown below:

Aryl group Yield Phenyl (1) 81% 2-methylphenyl (2) 75%2,5-dimethylphenyl (3) 75% 3,5-dimethylphenyl (4) 80% Napthyl (5) 77%2-methylnapthyl* (6) 49% *pinacol borane

The following schemes illustrate general methods for the preparation ofthe ligands.

Schemes 1 and 2 illustrate Suzuki coupling of a brominated phenol with abridged diboronic acid.

Schemes 3 and 4 illustrate tetrahalogenation of a bridged bi-aromaticphenol.

Schemes 5 and 6 illustrate Suzuki coupling of the tetrahalogenatedphenols with aryl boronic acid.

In any one of the above methods each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸,R⁹, R¹⁰, R¹¹ and R¹² may be independently selected from the groupconsisting of hydride and optionally substituted alkyl or aryl.

In any of the above methods Y and Y′ may be O.

In any of the above methods A may be selected from the group consistingof optionally substituted divalent alkyl, alkenyl, alkynyl, heteroalkyl,heteroalkenyl, heteroalkynyl, carbocycle, heterocarbocycle, aryl,heteroaryl and silyl.

In any of the above methods A may be optionally substituted alkyl.

In any of the above methods the palladium catalyst may comprise apalladium phosphine compound, for example,bis(tri-tert-butylphosphine)palladium (Pd(PPh₃)₄),tetrakis(triphenylphosphine)palladium(0) (Pd(dppe)₂),bis[1,2-bis(diphenylphosphino)ethane]palladium(0) (Pd(dppf)),1,1′-bis(diphenylphosphino)ferrocene palladium,(2,2′-bis(diphenylphosphino)-1,1′-binaphthyl palladium (Pd(BINAP).

In any of the above methods the palladium catalyst may comprise apalladium compound and one or more phosphines. For example,tris(dibenzylideneacetone)dipalladium(0) (Pd₂(dba)₃) and Pd(OAc)₂ andone or more phosphine compounds.

In any of the above methods X may be bromo or chloro. The source ofhalogen may be bromine or chlorine.

In any of the above methods the Ar-boron compound may be an optionallysubstituted aryl boronic acid or an optionally substituted heteroarylboronic acid.

In any of the above methods the Ar-boron compound may be an optionallysubstituted aryl boronic ester or an optionally substituted heteroarylboronic ester.

In any of the above methods the Ar-boron compound may be an optionallysubstituted aryl trifluoroborate or an optionally substituted heteroaryltrifluoroborate.

In any of the above methods the Ar-boron compound may be an optionallysubstituted arylborane or an optionally substituted heteroarylborane.

In any of the above methods a base may be utilized along with thepalladium catalyst.

In any of the above methods the base may comprise an alkali metalcarbonate, alkali metal phosphate, alkali metal hydroxide, alkali metalalkoxide or an amine.

The base may comprise sodium or potassium carbonate or sodium orpotassium phosphate.

In an illustrative embodiment and referring to the structures in FIG. 1and the reaction scheme in FIG. 3: treatment of1,3-bis(2-bromophenoxy)propane with n-butyllithium followed by trimethylborate and then HCl afforded(Propane-1,3-diylbisoxy)bis(2,1-phenylene)diboronic acid (9). Thediboronic acid, 2-bromocresol, SPhos, and potassium phosphate weredissolved in degassed THF and water, then stirred at ambient temperatureovernight to yield2′,2′″-(Propane-1,3-diylbis(oxy))bis(5-methyl-[1,1′-biphenyl]-2-ol)(10). The diphenolic compound (10) was dissolved in dichloromethane andtreated with bromine. The reaction was quenched with saturated sodiumbicarbonate to yield6′,6′″-(Propane-1,3-diylbisoxy)bis(3,3′-dibromo-5-methyl-[1,1′-biphenyl]-2-ol)(11). The brominated compound was combined with phenylboronic acid,SPhos and potassium phosphate in THF/H₂O and the mixture was stirred atroom temperature overnight to yield6″,6″″″-(Propane-1,3-diylbisoxy)bis(5′-methyl-[1,1′:3′,1″:3″,1′″-quaterphenyl]-2′-ol)(12).

FIGS. 4 and 5 illustrate other exemplary reaction schemes.

Catalyst Compounds

The catalyst compounds may be prepared by any suitable synthesis methodand the method of synthesis is not critical to the present disclosure.One useful method of preparing the catalyst compounds of the presentdisclosure is by reacting a suitable metal compound, for example onehaving a displaceable anionic ligand, with the bridged bi-aromaticligands of this disclosure. Non-limiting examples of suitable metalcompounds include organometallics, metal halids, sulfonates,carboxylates, phosphates, organoborates (including fluoro-containing andother subclasses), acetonacetonates, sulfides, sulfates,tetrafluoroborates, nitrates, perchlorates, phenoxides, alkoxides,silicates, arsenates, borohydrides, naphthenates, cyclooctadienes, dieneconjugated complexes, thiocynates, cyanates, and the metal cyanides. Themetal compound may be an organometallic or metal halide. The metalcompound may be an organometallic.

The metal of the organometallic compound may be selected from Groups 1to 16, or a transition metal selected from Groups 3 to 13 elements andLanthanide series elements. The metal may be selected from Groups 3 to 7elements. The metal may be a Group 4 metal, titanium, zirconium orhafnium.

The metal compound can, for example, be a metal hydrocarbyl such as: ametal alkyl, a metal aryl, a metal arylalkyl; a metal silylalkyl; ametal diene, a metal amide; or a metal phosphide. The metal compound maybe a zirconium or hafnium hydrocarbyl. The transition metal compound maybe a zirconium arylalkyl.

An exemplary reaction is shown below:

Examples of useful and preferred metal compounds include:

(i) tetramethylzirconium, tetraethylzirconium, zirconiumdichloride(η⁴-1,4-diphenyl-1,3-butadiene), bis (triethylphosphine) andzirconiumdichloride (η⁴-1,4-diphenyl-1,3-butadiene) bis(tri-n-propylphosphine), tetrakis[trimethylsilylmethyl]zirconium,tetrakis[dimethylamino]zirconium, dichlorodibenzylzirconium,chlorotribenzylzirconium, trichlorobenzylzirconium,bis[dimethylamino]bis[benzyl]zirconium, and tetrabenzylzirconium;(ii) tetramethyltitanium, tetraethyltitanium, titaniumdichloride(η⁴-1,4-diphenyl-1,3-butadiene), bis (triethylphosphine) andtitaniumdichloride (η⁴-1,4-diphenyl-1,3-butadiene) bis(tri-n-propylphosphine), tetrakis[trimethylsilylmethyl]titanium,tetrakis[dimethylamino]titanium, dichlorodibenzyltitanium,chlorotribenzyltitanium, trichlorobenzyltitanium,bis[dimethylamino]bis[benzyl]titanium, and tetrabenzyltitanium; and(iii) tetramethylhafnium, tetraethylhafnium, hafniumdichloride(η⁴-1,4-diphenyl-1,3-butadiene), bis (triethylphosphine) andhafniumdichloride (η⁴-1,4-diphenyl-1,3-butadiene) bis(tri-n-propylphosphine), tetrakis[trimethylsilylmethyl]hafnium,tetrakis[dimethylamino]hafnium, dichlorodibenzylhafnium,chlorotribenzylhafnium, trichlorobenzylhafnium,bis[dimethylamino]bis[benzyl]hafnium, and tetrabenzylhafnium.Catalyst and Supported Catalyst Compositions

The catalyst compositions disclosed herein may comprise one or morecatalyst compounds as disclosed herein and one or more activators asdisclosed herein.

The supported catalyst compositions as disclosed herein may comprise oneor more supports as disclosed herein, one or more catalyst compounds asdisclosed herein and one or more activators as disclosed herein.

The catalyst compositions and supported catalyst compositions maycomprise one or more of the catalyst compounds as hereinbefore disclosedalong with another catalyst compound, such as a metallocene catalystcompound or a Group V atom containing catalyst compound. Suitable othercatalyst compounds include, but are not limited to:

-   -   (pentamethylcyclopentadienyl)(propylcyclopentadienyl)MX₂,    -   (tetramethylcyclopentadienyl)(propylcyclopentadienyl)MX₂,    -   (tetramethylcyclopentadienyl)(butylcyclopentadienyl)MX₂,    -   Me₂Si(indenyl)₂MX₂,    -   Me₂Si(tetrahydroindenyl)₂MX₂,    -   (n-propyl cyclopentadienyl)₂MX₂,    -   (n-butyl cyclopentadienyl)₂MX₂,    -   (1-methyl, 3-butyl cyclopentadienyl)₂MX₂,    -   HN(CH₂CH₂N(2,4,6-Me₃phenyl))₂MX₂,    -   HN(CH₂CH₂N(2,3,4,5,6-Me₅phenyl))₂MX₂,    -   (propyl cyclopentadienyl)(tetramethylcyclopentadienyl)MX₂,    -   (butyl cyclopentadienyl)₂MX₂,    -   (propyl cyclopentadienyl)₂MX₂, and mixtures thereof,    -   wherein M is Zr or Hf, and X is selected from F, Cl, Br, I, Me,        benzyl, CH₂SiMe₃, and    -   C₁ to C₅ alkyls or alkenyls.

The supported catalyst composition may in the form of a substantiallydry powder or be in the form of a slurry in at least one liquid vehicle.Non-limiting examples of liquid vehicles include mineral oils, aromatichydrocarbons or aliphatic hydrocarbons.

Activator Compounds

An activator is defined in a broad sense as any combination of reagentsthat increases the rate at which a transition metal compoundoligomerizes or polymerizes unsaturated monomers, such as olefins. Thecatalyst compounds may be activated for oligomerization and/orpolymerization catalysis in any manner sufficient to allow coordinationor cationic oligomerization and/or polymerization.

Additionally, the activator may be a Lewis-base, such as for example,diethyl ether, dimethyl ether, ethanol, or methanol. Other activatorsthat may be used include those described in WO 98/07515 such as tris(2,2′,2″-nonafluorobiphenyl) fluoroaluminate.

Combinations of activators may be used. For example, alumoxanes andionizing activators may be used in combinations, see for example, EP-B10 573 120, WO 94/07928 and WO 95/14044 and U.S. Pat. Nos. 5,153,157 and5,453,410. WO 98/09996 describes activating metallocene catalystcompounds with perchlorates, periodates and iodates including theirhydrates. WO 98/30602 and WO 98/30603 describe the use of lithium(2,2′-bisphenyl-ditrimethylsilicate).4THF as an activator for ametallocene catalyst compound. WO 99/18135 describes the use oforgano-boron-aluminum activators. EP-B1-0 781 299 describes using asilylium salt in combination with a non-coordinating compatible anion.WO 2007/024773 suggests the use of activator-supports which may comprisea chemically-treated solid oxide, clay mineral, silicate mineral, or anycombination thereof. Also, methods of activation such as using radiation(see EP-B1-0 615 981), electro-chemical oxidation, and the like are alsocontemplated as activating methods for the purposes of rendering theneutral metallocene catalyst compound or precursor to a metallocenecation capable of polymerizing olefins. Other activators or methods foractivating a metallocene catalyst compound are described in, forexample, U.S. Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and PCT WO98/32775.

Alumoxanes may also be utilized as an activator in the catalystcomposition. Alumoxanes are generally oligomeric compounds containing—Al(R)—O— subunits, where R is an alkyl group. Examples of alumoxanesinclude methylalumoxane (MAO), modified methylalumoxane (MMAO),ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modifiedalkylalumoxanes are suitable as catalyst activators, particularly whenthe abstractable ligand is a halide. Mixtures of different alumoxanesand modified alumoxanes may also be used. For further descriptions, seeU.S. Pat. Nos. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199,5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032,5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP 0 561 476 A1, EP 0 279586 B1, EP 0 516 476 A, EP 0 594 218 A1 and WO 94/10180.

Alumoxanes may be produced by the hydrolysis of the respectivetrialkylaluminum compound. MMAO may be produced by the hydrolysis oftrimethylaluminum and a higher trialkylaluminum such astriisobutylaluminum. MMAO's are generally more soluble in aliphaticsolvents and more stable during storage. There are a variety of methodsfor preparing alumoxane and modified alumoxanes, non-limiting examplesof which are described in, for example, U.S. Pat. Nos. 4,665,208,4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018,4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081,5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253,5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 andEuropean publications EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218and EP-B1-0 586 665, WO 94/10180 and WO 99/15534. A visually clearmethylalumoxane may be used. A cloudy or gelled alumoxane can befiltered to produce a clear solution or clear alumoxane can be decantedfrom the cloudy solution. Another alumoxane is a modified methylalumoxane (MMAO) cocatalyst type 3A (commercially available from AkzoChemicals, Inc. under the trade name Modified Methylalumoxane type 3A,disclosed in U.S. Pat. No. 5,041,584).

An ionizing or stoichiometric activator, neutral or ionic, such as tri(n-butyl) ammonium tetrakis (pentafluorophenyl) boron, atrisperfluorophenyl boron metalloid precursor or a trisperfluoronapthylboron metalloid precursor, polyhalogenated heteroborane anions (see, forexample, WO 98/43983), boric acid (see, for example, U.S. Pat. No.5,942,459) or combinations thereof, may also be used. The neutral orionic activators may be used alone or in combination with alumoxane ormodified alumoxane activators.

Examples of neutral stoichiometric activators may includetri-substituted boron, tellurium, aluminum, gallium and indium ormixtures thereof. The three substituent groups may be each independentlyselected from the group of alkyls, alkenyls, halogen, substitutedalkyls, aryls, arylhalides, alkoxy and halides. The three substituentgroups may be independently selected from the group of halogen, mono ormulticyclic (including halosubstituted) aryls, alkyls, and alkenylcompounds and mixtures thereof; or alkenyl groups having 1 to 20 carbonatoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms(including substituted aryls). Alternatively, the three groups arealkyls having 1 to 4 carbon groups, phenyl, napthyl or mixtures thereof.The three groups may be halogenated, for example fluorinated, arylgroups. In yet other illustrative examples, the neutral stoichiometricactivator is trisperfluorophenyl boron or trisperfluoronapthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in, for example, Europeanpublications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157,5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124.

Supports

The above described catalyst compounds may be combined with one or moresupports using one of the support methods well known in the art or asdescribed below. For example, the catalyst compound may be used in asupported form, such as, deposited on, contacted with, or incorporatedwithin, adsorbed or absorbed in, or on the support.

As used herein, the term “support” refers to compounds comprising Group2, 3, 4, 5, 13 and 14 oxides and chlorides. Suitable supports include,for example, silica, magnesia, titania, zirconia, montmorillonite,phyllosilicate, alumina, silica-alumina, silica-chromium,silica-titania, magnesium chloride, graphite, magnesia, titania,zirconia, montmorillonite, phyllosilicate, and the like.

The support may possess an average particle size in the range of fromabout 0.1 to about 500 μm, or from about 1 to about 200 μm, or fromabout 1 to about 50 μm, or from about 5 to about 50 μm.

The support may have an average pore size in the range of from about 10to about 1000 {acute over (Å)}, or about 50 to about 500 {acute over(Å)}, or 75 to about 350 {acute over (Å)}.

The support may have a surface area in the range of from about 10 toabout 700 m²/g, or from about 50 to about 500 m²/g, or from about 100 toabout 400 m²/g.

The support may have a pore volume in the range of from about 0.1 toabout 4.0 cc/g, or from about 0.5 to about 3.5 cc/g, or from about 0.8to about 3.0 cc/g.

The support, such as an inorganic oxide, may have a surface area in therange of from about 10 to about 700 m²/g, a pore volume in the range offrom about 0.1 to about 4.0 cc/g, and an average particle size in therange of from about 1 to about 500 μm. Alternatively, the support mayhave a surface area in the range of from about 50 to about 500 m²/g, apore volume of from about 0.5 to about 3.5 cc/g, and an average particlesize of from about 10 to about 200 μm. The surface area of the supportmay be in the range from about 100 to about 400 m²/g, a pore volume offrom about 0.8 to about 3.0 cc/g and an average particle size of fromabout 5 to about 100 μm.

The catalyst compounds may be supported on the same or separate supportstogether with an activator, or the activator may be used in anunsupported form, or may be deposited on a support different from thesupported catalyst compound.

There are various other methods in the art for supporting apolymerization catalyst compound. For example, the catalyst compound maycontain a polymer bound ligand as described in, for example, U.S. Pat.Nos. 5,473,202 and 5,770,755; the catalyst may be spray dried asdescribed in, for example, U.S. Pat. No. 5,648,310; the support usedwith the catalyst may be functionalized as described in Europeanpublication EP-A-0 802 203, or at least one substituent or leaving groupis selected as described in U.S. Pat. No. 5,688,880.

Polymerization Processes

Polymerization processes may include solution, gas phase, slurry phaseand a high pressure process or a combination thereof. In illustrativeembodiments, a gas phase or slurry phase polymerization of one or moreolefins at least one of which is ethylene or propylene is provided.Optionally, the reactor is a gas phase fluidized bed polymerizationreactor.

The catalyst compositions or supported catalyst compositions ashereinbefore described are suitable for use in any prepolymerizationand/or polymerization process over a wide range of temperatures andpressures. The temperatures may be in the range of from −60° C. to about280° C., from 50° C. to about 200° C.; from 60° C. to 120° C. from 70°C. to 100° C. or from 80° C. to 95° C.

The present process may be directed toward a solution, high pressure,slurry or gas phase polymerization process of one or more olefinmonomers having from 2 to 30 carbon atoms, preferably 2 to 12 carbonatoms, and more preferably 2 to 8 carbon atoms. The process isparticularly well suited to the polymerization of two or more olefins orcomonomers such as ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, 1-octene 1-decene or the like.

Other olefins useful in the present process include ethylenicallyunsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugatedor nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins.Useful monomers may include, but are not limited to, norbornene,norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes,alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene andcyclopentene. In an illustrative embodiment of the present process, acopolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 4 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a gas phase process. In anotherembodiment of the present process, ethylene or propylene is polymerizedwith at least two different comonomers, optionally one of which may be adiene, to form a terpolymer.

The present process may be directed to a polymerization process,particularly a gas phase or slurry phase process, for polymerizingpropylene alone or with one or more other monomers including ethylene,and/or other olefins having from 4 to 12 carbon atoms. Thepolymerization process may comprise contacting ethylene and optionallyan alpha-olefin with one or more of the catalyst compositions orsupported catalyst compositions as hereinbefore described in a reactorunder polymerization conditions to produce the ethylene polymer orcopolymer.

Suitable gas phase polymerization processes are described in, forexample, U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036,5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661,5,668,228, 5,627,242, 5,665,818, and 5,677,375, and Europeanpublications EP-A-0 794 200, EP-A-0 802 202, EP-A2 0 891 990, andEP-B-634 421.

A slurry polymerization process generally uses pressures in the range offrom about 1 to about 50 atmospheres and even greater and temperaturesin the range of 0° C. to about 120° C. In a slurry polymerization, asuspension of solid, particulate polymer is formed in a liquidpolymerization diluent medium to which ethylene and comonomers and oftenhydrogen along with catalyst are added. The suspension including diluentis intermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

A preferred polymerization process is referred to as a particle formpolymerization, or a slurry process where the temperature is kept belowthe temperature at which the polymer goes into solution. Such techniqueis well known in the art, and described in for instance U.S. Pat. No.3,248,179. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. No. 4,613,484. Examplesof solution processes are described in U.S. Pat. Nos. 4,271,060,5,001,205, 5,236,998 and 5,589,555.

EXAMPLES

It is to be understood that while the present disclosure has beendescribed in conjunction with the specific embodiments thereof, theforegoing description is intended to illustrate and not limit the scopeof the disclosure. Other aspects, advantages and modifications will beapparent to those skilled in the art to which the disclosure pertains.Therefore, the following examples are put forth so as to provide thoseskilled in the art with a complete disclosure and description of how tomake and use the disclosed compositions, and are not intended to limitthe scope of the disclosure.

General:

All reagents were purchased from commercial vendors and used as receivedunless otherwise noted. Analytical thin-layer chromatography (TLC) wasperformed on Selecto Plates (200 m) precoated with a fluorescentindicator. Visualization was effected using ultraviolet light (254 nm).Flash column chromatography was carried out with Sigma Aldrich Silicagel 60 Å (70-230 Mesh). NMR spectra were recorded on a Bruker 400 NMRwith chemical shifts referenced to residual solvent peaks (CDCl₃: 7.27ppm for ¹H, 77.29 ppm for ¹³C; C₆D₆: 7.15 ppm for ¹H, 77.39 ppm for¹³C). Melting points are reported uncorrected. Abbreviations:SPhos—Chloro(2-dicyclohexylphosphino-2′,6′-dimethoxy-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II);PTSA—para-toluenesulfonic acid.

General Procedure for Suzuki Coupling:

In an appropriately sized flask, 2-Bromo-p-cresol (1 equiv), arylboronic acid (1.5 equiv) and palladium tetrakistriphenylphosphine (0.02equiv) were dissolved in degassed toluene to make a 0.2 M solution withrespect to the cresol. A 2 M solution of sodium carbonate (4 equiv) indegassed H₂O:MeOH (4:1) was added and the mixture refluxed untilcompletion (usually overnight). The reaction was cooled and the layersseparated. The aqueous layer was extracted twice with ethyl acetate andcombined organic layers were washed with brine, dried over MgSO₄ orNa₂SO₄, filtered, and concentrated under reduced pressure.

5-Methyl-[1,1′-biphenyl]-2-ol (1)

Using the above general procedure, a white solid was isolated by columnchromatography in 81% yield: ¹H NMR (400 MHz, C₆D₆, δ): 2.10 (s, 3H),6.69 (m, 3H), 7.12 (m, 2H), 7.15 (m, 1H), 7.35 (m, 2H).

2′,5-Dimethyl-[1,1′-biphenyl]-2-ol (2)

Using the above general procedure, a white solid was isolated by columnchromatography (30:70 actone:isohexane) in 75% yield: R_(f)=0.25 (30:70acetone:isohexane); ¹H NMR (400 MHz, CDCl₃, δ): 2.20 (s, 3H), 2.33 (s,3H), 4.65 (br s, 1H), 6.70 (d, J=6.8 Hz, 1H), 6.94 (s, 1H), 7.10 (m,1H), 7.33 (m, 4H).

3′,5,5′-Trimethyl-[1,1′-biphenyl]-2-ol (3)

Using the above general procedure, a white solid was isolated by columnchromatography (30:70 actone:isohexane) in 75% yield: R_(f)=0.32 (20:80acetone:isohexane); ¹H NMR (400 MHz, CDCl₃, δ): 2.34 (s, 3H), 2.41 (s,6H), 5.19 (br s, 1H), 6.91 (d, J=8.4 Hz, 1H), 7.08 (m, 5H).

2′,5,5′-Trimethyl-[1,1′-biphenyl]-2-ol (4)

Using the above general procedure, a white solid was isolated by columnchromatography (10% acetone/isohexane) in 80% yield: R_(f)=0.26 (10:90acetone:isohexane); H NMR (400 MHz, CDCl₃, δ): 2.15 (s, 3H), 2.32 (s,3H), 2.36 (s, 3H), 4.66 (br s, 1H), 6.89 (d, J=8.4 Hz, 1H), 6.93 (m,1H), 7.07 (m, 2H), 7.21 (m, 1H), 7.26 (m, 1H).

4-Methyl-2-(naphthalen-1-yl)phenol (5)

Using the above general procedure, the product was isolated by columnchromatography (30% actone:isohexane) in 77% yield as a pale yellow oil:¹H NMR (500 MHz, CDCl₃, 6): 2.37 (s, 3H), 4.67 (s, 1H), 6.98 (d, J=9 Hz,1H), 7.09 (s, 1H), 7.09 (m, 1H), 7.56 (m, 4H), 7.70 (d, J=8 Hz, 1H),7.93 (m, 2H); ¹³C NMR (100 MHz, CDCl₃, δ): 20.8, 115.6, 126.0-134.5(14C), 151.2; IR (cm⁻¹): 3519, 3045, 2920, 1590, 1496, 1333, 1276, 1183,781.

4-Methyl-2-(2-methylnaphthalen-1-yl)phenol (6)

Following the above general procedure, substituting 2-methylnapthylpinacol borane for the aryl boronic acid, the product was purified bysilica gel chromatography (10% acetone/isohexane) in 49% yield as a paleyellow oil which solidified upon standing. R_(f)=0.32 (30:70acetone:isohexane); ¹H NMR (400 MHz, CDCl₃, δ): 2.29 (s, 3H), 2.36 (s,3H), 4.42 (s, 1H), 6.95 (s, 1H), 7.00 (d, J=4.0 Hz, 1H), 7.19 (d, J=8Hz, 1H), 7.44 (m, 4H), 7.86 (t, J=8.0 Hz, 2H); ¹³C NMR (100 MHz, CDCl₃,6): 20.7, 20.8, 115.4, 125.0, 125.5, 125.8, 126.8, 128.2, 128.7, 129.0,130.1, 130.2, 131.5, 131.6, 132.5, 133.2, 135.8, 151.1; IR (cm⁻¹): 3498,3426, 3050, 2922, 2860, 1617, 1594, 1497, 1335, 1275, 1228, 1188, 814.

3-Bromo-3′,5,5′-trimethyl-[1,1′-biphenyl]-2-ol (7)

Phenol (3) (1 g, 4.7 mmol) was dissolved in methylene chloride andcooled to −35° C. Bromine (0.3 mL, 5.6 mmol) was slowly added and thesolution stirred at ambient temperature overnight. The reaction wasquenched with saturated sodium bicarbonate solution and extracted 3times with methylene chloride. The combined organic portions were washedwith sodium metabisulfite and brine, then dried over MgSO₄, filtered,and concentrated. R_(f)=0.30 (10:90 ethyl acetate:isohexane); ¹H NMR(400 MHz, CDCl₃, δ): 2.33 (s, 3H), 2.49 (s, 6H), 5.07 (br s, 1H), 6.87(d, J=8.4 Hz, 1H), 7.03 (m, 2H), 7.19 (s, 2H); ¹³C NMR (100 MHz, CDCl₃,δ): 24.7 (2C), 25.2, 115.1, 127.4, 128.4, 129.1, 129.9, 130.3, 130.8,131.6, 136.0, 139.4, 139.5, 150.3; IR (cm⁻¹): 3533, 2921, 1499, 1464,1381, 1237, 1029, 814.

(Butane-1,4-diylbis(oxy))bis(2,1-phenylene)diboronic acid (8)

To 1,4-bis(2-bromophenoxy)butane (5 g, 12.5 mmol) dissolved in 40 mLTHF, was added n-butyllithium (11 mL of 2.5 M). The reddish brownsolution was stirred cold for 2 h. Trimethyl borate (5.6 mL, 50 mmol)was added as the solution slowly turned colorless and was stirredovernight at ambient temperature. The reaction was quenched with conc.HCl and condensed to a white solid. The solid was washed with ether togive the diboronic acid in 68% yield: ¹H NMR (400 MHz, DMSO-d₆, δ): 1.92(app br s, 4H), 4.10 (app br s, 4H), 6.93 (t, J=8.0 Hz, 2H), 7.00 (d,J=8.0 Hz, 2H), 7.36 (m, 2H), 7.55 (m, 2H), 7.72 (s, 4H).

(Propane-1,3-diylbisoxy)bis(2,1-phenylene)diboronic acid (9)

1,3-bis(2-bromophenoxy)propane (3.1 g, 8 mmol) was prepared according toestablished procedures and dissolved in 10 mL THF, then cooled to −70°C. n-Butyllithium (6.4 mL of 2.5 M) was added and the deep red reactionstirred for 1 h. Trimethyl borate (3.5 mL, 24 mmol) was added as thesolution slowly turned colorless and warmed to ambient temperature over1 h. The reaction was quenched with 10% HCl and extracted with threeportions of ether. The combined organic layers were washed with brine,dried over Na₂SO₄, and concentrated. The product was recrystallized indichloromethane, giving a white powder: ¹H NMR (400 MHz, DMSO, δ): 2.25(m, 2H), 4.19 (m, 4H), 6.93 (m, 2H), 6.99 (d, J=8.0 Hz, 2H), 7.36 (m,2H), 7.53 (m, 2H), 7.74 (m, 2H); ¹³C NMR (100 MHz, DMSO-d₆, δ): 28.7,64.1, 65.0, 111.2 (2C), 114.5 (2C), 120.5, 120.6, 131.5 (2C), 138.4(2C).

2′,2′″-(Propane-1,3-diylbis(oxy))bis(5-methyl-[1,1′-biphenyl]-2-ol) (10)

The above diboronic acid (600 mg, 1.89 mmol), 2-bromocresol (800 mg, 4.2mmol), SPhos (50 mg, 0.07 mmol), and potassium phosphate (1.6 g, 7.56mmol) were dissolved in degassed THF and water, then stirred at ambienttemperature overnight. The reaction mixture was extracted with 4portions of ether and the combined organic layers washed with brine,dried (Na₂SO₄), filtered and concentrated. Column chromatography (30%acetone/isohexane eluent) gave the cross-coupled product in 74% yield asa pale yellow oil: R_(f)=0.37 (acetone/isohexane 30:70); ¹H NMR (400MHz, CDCl₃, δ): 2.11 (qn, J=6.0 Hz, 2H), 2.33 (s, 6H), 4.10 (t, J=6.0Hz, 4H), 6.02 (s, 2H), 6.91 (m, 4H), 7.05 (m, 2H), 7.14 (m, 4H), 7.35(m, 4H); ¹³C NMR (100 MHz, CDCl₃, δ): 20.7 (2C), 28.9, 65.8 (2C), 113.5(2C), 117.0 (2C), 122.6 (2C), 126.0 (2C), 127.7 (2C), 129.4 (2C), 129.9(2C), 130.1 (2C), 131.8 (2C), 132.4 (2C), 151.5 (2C), 154.9 (2C); IR(cm⁻¹): 4307, 3028, 2923, 1597, 1499, 1445, 1270, 1229, 1113, 1054, 909,818.

6′,6′″-(Propane-1,3-diylbisoxy)bis(3,3′-dibromo-5-methyl-[1,1′-biphenyl]-2-ol)(11)

The above diphenolic compound (620 mg, 1.38 mmol) was dissolved in 40 mLdichloromethane. Bromine (0.178 mL, 3.47 mmol) was added slowly and thereaction stirred at room temperature for 1 h. The reaction was quenchedwith saturated sodium bicarbonate, and the organic layer washed withsodium metabisulfite and brine, then dried (Na₂SO₄), filtered andconcentrated. The tetrabrominated compound was recrystallized in ether:¹H NMR (400 MHz, CDCl₃, δ): 2.05 (qn, J=6.0 Hz, 2H), 2.23 (s, 6H), 4.00(t, J=6.0 Hz, 4H), 5.72 (s, 2H), 6.81 (d, J=8.0 Hz, 2H), 6.87 (d, J=4Hz, 2H), 7.30 (d, J=4.0 Hz, 2H), 7.37 (d, J=4.0 Hz, 2H), 7.45 (m, 2H);¹³C NMR (100 MHz, CDCl₃, δ): 20.5 (2C), 28.6, 65.2 (2C), 111.0 (2C),114.0 (2C), 114.7 (2C), 126.8 (2C), 129.1 (2C), 131.4 (4C), 132.4 (2C),132.9 (2C), 134.4 (2C), 147.9 (2C), 154.6 (2C); IR (cm¹): 3500, 2924,1588, 1472, 1387, 1280, 1234, 1127, 1085, 808.

6″,6″″″-(Propane-1,3-diylbisoxy)bis(5′-methyl-[1,1′:3′,1″:3″,1′″-quaterphenyl]-2′-ol)(12)

The above brominated compound (420 mg, 0.55 mmol) was combined withphenylboronic acid (304 mg, 2.49 mmol), SPhos (40 mg, 0.055 mmol) andpotassium phosphate (583 mg, 2.75 mmol) in 40 mL of degassed THF/H₂O.The mixture was stirred at room temperature overnight, and thenextracted with 2 portions of ether. The combined organic layers werewashed with brine, dried (Na₂SO₄), filtered and concentrated. Theresidue was purified by column chromatography giving the phenylatedproduct as a pale yellow solid: mp=82-89° C.; R_(f)=0.44(acetone/isohexane 30:70); ¹H NMR (400 MHz, CD₂Cl₂, δ): 2.17 (m, 2H),2.34 (s, 6H), 4.18 (t, J=8.0 Hz, 4H), 5.8 (s, 2H), ¹³C NMR (100 MHz,CD₂Cl₂, δ): 20.8 (2C), 29.4, 65.9 (2C), 113.7 (2C), 127.0-131.7 (36C),135.3 (2C), 139.3 (2C), 140.8 (2C), 148.7 (2C), 155.3 (2C).

Zr Complex (13)

The above diphenol (200 mg, 0.268 mmol) was dissolved in 15 mL tolueneand cooled to −35° C. Dibenzylzirconium dichloride (105 mg, 0.268 mmol)was added and the reaction heated at 60° C. until a precipitate formed(approx. 3 h). Toluene was removed and the solid washed with hexanegiving the zirconium complex as a pale cream colored powder: ¹H NMR (400MHz, CD₂Cl₂, δ): 1.53 (m, 2H), 2.34 (s, 3H), 2.38 (s, 3H), 3.76 (m, 2H),4.15 (m, 2H), 7.14-7.89 (m, 30H).

2′,2′″-(Butane-1,4-diylbisoxy)bis(5-methyl-[1,1′-biphenyl]-2-ol) (14)

Diboronic acid (3 g, 9.1 mmol), 2-bromocresol (3.4 g, 18.1 mmol), SPhos(130 mg, 0.18 mmol), and potassium phosphate (7.7 g, 36 mmol) weredissolved in 200 mL THF/H₂O and stirred at ambient temperatureovernight. The layers were separated and the aqueous layer extractedtwice with ether. The combined organic layers were washed with 10% HCland brine, then dried (Na₂SO₄), filtered and concentrated. The brownresidue was purified by silica gel column chromatography (30% ethylacetate/isohexane), giving the product as a pale yellow oil: ¹H NMR (400MHz, CDCl₃, δ): 1.81 (m, 4H), 2.31 (s, 6H), 3.98 (m, 4H), 6.22 (s, 2H),6.88 (m, 4H), 7.03 (m, 6H), 7.32 (m, 4H); ¹³C NMR (100 MHz, CDCl₃, 6):20.8 (2C), 25.9 (2C), 69.3 (2C), 113.5 (2C), 117.4 (2C), 122.6 (2C),126.4 (2C), 128.1 (2C), 129.3 (2C), 130.0 (2C), 130.2 (2C), 131.9 (2C),132.7 (2C), 151.7 (2C), 155.0 (2C); IR (cm¹): 3397, 3027, 2945, 1597,1499, 1444, 1268, 1229, 1112, 818.

6′,6′″-(Butane-1,4-diylbis(oxy))bis(3,3′-dibromo-5-methyl-[1,1′-biphenyl]-2-ol)(15)

The above diphenolic compound (700 mg, 1.5 mmol) and triethylamine (0.30mL, 2.2 mmol) were dissolved in 10 mL dichloromethane. Bromine (0.095mL, 1.84 mmol) was added slowly and the reaction stirred at roomtemperature overnight. The reaction was quenched with saturated sodiumbicarbonate, and the organic layer washed with sodium metabisulfite andbrine, then dried (Na₂SO₄), filtered and concentrated. The resultingwhite powder was obtained in 95% yield by recrystallization in ether: ¹HNMR (400 MHz, CDCl₃, δ): 1.75 (m, 4H), 2.27 (s, 6H), 3.93 (m, 4H), 5.99(s, 2H), 6.79 (d, J=12.0 Hz, 2H), 6.94 (m, 2H), 7.40 (m, 2H), 7.45 (m,4H); ¹³C NMR (125 MHz, CDCl₃, δ): 20.5 (2C), 25.8 (2C), 69.1 (2C), 111.3(2C), 114.1 (2C), 114.8 (2C), 125.8 (2C), 129.4 (2C), 131.3 (2C), 131.5(2C), 132.2 (2C), 132.9 (2C), 134.6 (2C), 148.0 (2C), 155.0 (2C).

6″,6″″″-(Butane-1,4-diylbisoxy)bis(2,2′″,5,5′,5′″-pentamethyl-[1,1′:3′,1″:3″,1′″-quaterphenyl]-2′-ol)(16)

The above brominated compound (700 mg, 0.908 mmol) was combined with2,5-dimethylphenylboronic acid (613 mg, 4.1 mmol), SPhos (64 mg, 0.09mmol) and potassium phosphate (1.5 g, 7.2 mmol) in 80 mL of degassedTHF/H₂O. The mixture was stirred at room temperature overnight, and thenextracted with 2 portions of ether. The combined organic layers werewashed with brine, dried (Na₂SO₄), filtered and concentrated. Theresidue was purified by column chromatography giving the phenylatedproduct as a pale yellow solid: ¹H NMR (400 MHz, CDCl₃, δ): 1.83 (m,4H), 2.16-2.36 (m, 30H), 4.03 (4H), 5.96 (s, 2H), 6.95 (m, 4H), 7.07 (m,10H), 7.28 (m, 2H), 7.36 (m, 2H); ¹³C NMR (100 MHz, CDCl₃, 6): 20.4-23.5(10C), 26.7 (2C), 69.8 (2C), 113.5 (2C), 118.2 (2C), 126.9-141.8 (42C),149.2 (2C), 154.9 (2C); IR (cm¹): 3539, 3384, 3015, 2920, 1609, 1493,1461, 1382, 1228, 908, 811.

Zr Complex (17)

To compound (16) (200 mg, 0.23 mmol) dissolved in 15 mL toluene, wasadded dibenzylzirconium dichloride (90 mg, 0.23 mmol) at −35° C. Themixture was heated at 70° C. for 3 h, then concentrated to an oil. Upondissolving the oil in hexane, a while solid precipitated and was washedwith pentane: ¹H NMR (400 MHz, CD₂Cl₂, δ): 1.41 (m, 4H), 2.26-2.47 (m,30H), 4.13 (m, 2H), 4.54 (m, 2H), 5.95 (d, J=8.0 Hz, 2H), 7.30 (m, 22H).

6′,6′″-(Butane-1,4-diylbisoxy)bis(5-methyl-3,3′-di(naphthalen-1-yl)-[1,1′-biphenyl]-2-ol)(18)

Brominated compound (15) (400 mg, 0.519 mmol) was combined with2-naphthylboronic acid (402 mg, 2.3 mmol), palladiumtetrakistriphenylphosphine (30 mg, 0.025 mmol) and sodium carbonate (770mg, 7.26 mmol) in 20 mL of degassed tol/H₂O. The mixture was heated at90° C. overnight, and then extracted with 2 portions of ether. Thecombined organic layers were washed with brine, dried (Na₂SO₄), filteredand concentrated. The residue was purified by column chromatography (20%acetone/isohexane) giving the tetranaphthylated product as a whitepowder in 52% yield: ¹H NMR (400 MHz, CDCl₃, δ): 1.9 (m, 4H), 2.31 (s,6H), 4.04 (m, 4H), 7.00 (m, 2H), 7.10 (m, 2H), 7.21 (m, 2H), 7.50 (m,16H), 7.62 (m, 2H), 7.91 (m, 10H), 8.03 (d, J=12.4 Hz, 2H); ¹³C NMR (100MHz, CDCl₃, δ): 20.7 (2C), 23.1, 26.2, 69.3 (2C), 112.9 (2C),125.6-134.4 (52C), 134.8 (2C), 137.1 (2C), 139.8 (2C), 149.3 (2C), 154.7(2C); IR (cm⁻¹): 3393, 3043, 2950, 1710, 1600, 1497, 1465, 1226, 779.

Zr Complex (19)

Ligand (18) (200 mg, 0.208 mmol) was dissolved in 15 mL toluene andcooled to −35° C. Dibenzylzirconium dichloride (82 mg, 0.208 mmol) wasadded and the reaction heated at 90° C. until a precipitate formed(approx. 3 h). Toluene was removed and the solid washed with hexanegiving the zirconium complex as a white powder: ¹H NMR (500 MHz, tol-d₈,90° C., δ): 1.64 (m, 4H), 2.12 (s, 3H), 2.17 (s, 3H), 3.72 (m, 4H), 5.51(s, 1H), 6.78 (d, J=8.5 Hz, 2H), 7.06 (m, 2H), 7.30 (m, 19H), 7.64 (m,10H), 7.87 (d, J=8.5 Hz, 2H), 8.06 (d, J=8.5 Hz, 2H).

General Procedure for Supporting Catalysts:

The zirconium complex, typically between 15 to 30 mg, was dissolved intoluene and a solution of methylalumoxane (MAO; Albemarle, 30 wt. % intoluene) added. Silica gel (Grace-Davison 757 pretreated at 600° C.) wasadded and the slurry stirred until completely mixed (approximately 5minutes). Toluene was then removed under vacuum to give a dry freeflowing powder.

Laboratory Polymerization Tests

A 2 L autoclave was charged with fine granular sodium chloride under aninert N₂ atmosphere. 5 g of methylalumoxane treated silica was added tothe reactor by pressuring it in with a N₂ push. The reactor temperaturewas set to 85° C. The reactor was composed with hydrogen, 1-hexene andethylene such that the set-point reactor pressure was 220 psig and the1-hexene/ethylene mole ratio set. A pre-weighed charge of catalyst,between 10-15 mg, was pressured into the reactor. The pressure set-pointof the reactor was set to 220 psig. Ethylene was fed to the reactor tomaintain this set-point. H₂ and 1-hexene were also fed to the reactorsuch that their set-point concentration and C₆/C₂ ratio, respectively,were maintained. After one hour of run time, the polymer product wasrecovered and weighed.

The below Table collects the results of polymerization tests and polymercharacterization:

Zirconium C6/C2 Productivity Mw/ Recovery Compound Ratio [g/g cat] Mn MwMz Mn % Me (13) 0.1000 2061 214020 642307 1414075 3.0 81.4 21.5 (17)0.0800 3340 231817 776061 2055128 3.35 21.1 15.1 (17) 0.0150 1665 6480271279746 2135760 1.97 100.8 2.2 (19) 0.1200 5182 292927 1039138 27039663.55 14 21.1 (19) 0.0200 3302 799696 1524295 2427565 1.91 49.6 4.1

All of the catalysts showed good productivity and made high molecularweight ethylene-1-hexene copolymers. ‘Recovery %’ refers to the %polymer recovered from the reactor. ‘Me’ refers to the number of shortchain branch end groups as measured by NMR spectroscopy.

For the sake of brevity, only certain ranges are explicitly disclosedherein. However, ranges from any lower limit may be combined with anyupper limit to recite a range not explicitly recited, as well as, rangesfrom any lower limit may be combined with any other lower limit torecite a range not explicitly recited, in the same way, ranges from anyupper limit may be combined with any other upper limit to recite a rangenot explicitly recited.

All documents cited are herein fully incorporated by reference for alljurisdictions in which such incorporation is permitted and to the extentsuch disclosure is consistent with the description of the presentdisclosure.

What is claimed is:
 1. A catalyst composition comprising one or moretransition metal compounds comprising a bridged bi-aromatic phenolligand of formula (I);

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² isindependently selected from the group consisting of hydride, halide,optionally substituted hydrocarbyl, heteroatom-containing optionallysubstituted hydrocarbyl, alkoxy, aryloxy, silyl, boryl, dialkyl amino,alkylthio, arylthio and seleno; optionally two or more R groups cancombine together into ring structures with such ring structures havingfrom 3 to 100 non-hydrogen atoms in the ring; A is an optionallysubstituted divalent alkyl, alkenyl, alkynyl, heteroalkyl,heteroalkenyl, heteroalkynyl, carbocycle, heterocarbocycle, aryl,heteroaryl, or silyl; Y and Y′ are independently selected from O, S,NR^(a) and PR^(a) wherein R^(a) is optionally substituted hydrocarbyl;Ar is, independently, optionally substituted aryl or optionallysubstituted heteroaryl; and one or more activators.
 2. A catalystcomposition according to claim 1 wherein the one or more activators ismethylalumoxane.
 3. A supported catalyst composition comprising one ormore transition metal compounds according to claim 1, one or moreactivators and one or more support materials.
 4. A supported catalystcomposition according to claim 3 wherein the one or more activators ismethylalumoxane.
 5. A catalyst composition or supported catalystcomposition according to claim 1 further comprising one or more othertransition metal compounds.
 6. A process for polymerizing olefins, theprocess comprising: contacting olefins with one or more catalystcompositions or supported catalyst compositions according to claim 1 ina reactor under polymerization conditions to produce an olefin polymeror copolymer.
 7. The catalyst composition of claim 1, wherein thetransition metal compound according comprises a titanium, a zirconium ora hafnium atom.
 8. The catalyst composition of claim 1, wherein thebridged bi-aromatic phenol ligand has the structure of formula (II):

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² isindependently selected from the group consisting of hydride, halide,optionally substituted hydrocarbyl, heteroatom-containing optionallysubstituted hydrocarbyl, alkoxy, aryloxy, silyl, boryl, dialkyl amino,alkylthio, arylthio and seleno; optionally two or more R groups cancombine together into ring structures with such ring structures havingfrom 3 to 100 non-hydrogen atoms in the ring; A is an optionallysubstituted divalent alkyl, alkenyl, alkynyl, heteroalkyl,heteroalkenyl, heteroalkynyl, carbocycle, heterocarbocycle, aryl,heteroaryl, or silyl; Ar is, independently, optionally substituted arylor optionally substituted heteroaryl.
 9. The catalyst composition ofclaim 1, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹²are independently selected from the group consisting of hydride, halide,and optionally substituted alkyl, heteroalkyl, aryl, heteroaryl,alkoxyl, aryloxyl, silyl, boryl, dialkylamino, alkylthio, arylthio, andseleno.
 10. The catalyst composition of claim 1, wherein R¹, R², R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² are independently selected from thegroup consisting of hydride, halide, and optionally substituted alkyl,heteroalkyl, aryl, heteroaryl, alkoxyl, and aryloxyl.
 11. The catalystcomposition of claim 1, wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹ and R¹² are independently selected from the group consisting ofhydride, and optionally substituted alkyl, heteroalkyl, aryl, andheteroaryl.
 12. The catalyst composition of claim 1, wherein thebridging group A is selected from the group consisting of optionallysubstituted divalent hydrocarbyl and divalent heteroatom containinghydrocarbyl.
 13. The catalyst composition of claim 1, wherein thebridging group A is selected from the group consisting of optionallysubstituted divalent alkyl, alkenyl, alkynyl, heteroalkyl,heteroalkenyl, heteroalkynyl, aryl, heteroaryl and silyl.
 14. Thecatalyst composition of claim 1, wherein the bridging group A isrepresented by the general formula -(QR¹³ _(2−z″))_(z′)- wherein each Qis either carbon or silicon and each R¹³ may be the same or differentfrom the others such that each R¹³ is selected from the group consistingof hydride and optionally substituted hydrocarbyl and heteroatomcontaining hydrocarbyl, and optionally two or more R¹³ groups may bejoined into a ring structure having from 3 to 50 atoms in the ringstructure not counting hydrogen atoms; z′ is an integer from 1 to 10;and z″ is 0, 1 or
 2. 15. The catalyst composition of claim 1, wherein Aris, independently, an optionally substituted aryl or heteroaryl.
 16. Thecatalyst composition of claim 1, wherein Ar is, independently, anoptionally substituted phenyl, naphthyl, biphenyl, anthracenyl orphenanthrenyl.
 17. The catalyst composition of claim 1, wherein Ar is,independently, an optionally substituted thiophene, pyridine, isoxazole,pyrazole, pyrrole, furan, or benzo-fused analogues of these rings. 18.The catalyst composition of claim 1, wherein each occurrence of Ar isthe same.